Method for improving fabric strength in wash and wear treatments



United States Patent U.S. Cl. 8120 20 Claims ABSTRACT OF THE DISCLOSURE Crease-resistant cellulosic fabrics crosslinked with polyepoxides have improved strength when the croslinking is conducted in the presence of organic thiooxy compound containing an u,fi-thioalkoxy group,

Z-mercaptoalkanols, 2-hydroxyalkyl thioethers and their esters, for example, 2,2-thiodiethanol, Z-mercaptoethanol, 2,2'-(isobutylidenedithio)diethanol and 2,2-thiodiethanol diacetate.

This invention relates broadly to wash and 'wear treatments of cellulosic fabrics with polyepoxides. More particularly, this invention is concerned with improving the strength of cellulosic fabrics which have been treated with polyepoxides to improve their wash and wear characterlstics.

The use of polyepoxidcs to crosslink and thereby im- DIOV6 the wash and wear characteristics of cellulosic fabrics, such as cotton, rayon and the like, is a Wellknown technique, In general, the fabric is impregnated with an aqueous medium containing the polyepoxide and an acidic curing catalyst and the impregnated fabric is thereafter cured by heating at elevated temperatures. Impregnation is generally effected by immersing the fabric in an aqueous bath which, in addition to the epoxide and catalyst, may contain suspennding agents or emulsifiers, fabric softeners and other additives to modify the properties of the cured fabric.

One serious drawback to treatments of this type is the fact that the strength of the cured fabric is considerably less than that of the original fabric, often being as low as 50 percent of the original fabric or even lower. It has been discovered by this invention, however, that if the fabric is also impregnated with an organic thiooxy compound, as hereinafter defined, prior to curing, there is a marked increase in strength of the curved fabric, which, in some instances, may provide the treated fabric with a strength equivalent to that of the original fabric.

The organic thiooxy compounds which are employed in accordance with this invention are those acyclic aliphatic compounds containing at least one a,6-thioalkoxy group, i.e. compounds containing the group wherein the free valences are to hydrogen atoms or organic radicals. More specifically, suitable thiooxy compounds include 2-mercaptoalkanols and 2-hydroxyalkyl thioethers of the general formula:

(I) uoastea si aoa n wherein m and n each independently is an integer having a value of from 0 to 1; R is an a s-alkanediyl group of from 2 to about 6, prefreably 2 to 3, carbons; and R is an alkanediyl group of from 1 to about 10, preferably 1 to about 6 carbons. By the term alkanediyl group is meant a divalent, saturated, acyclic, hydrocarbon group,

ice

and by the term a,/3-alkanediyl group is meant an alkanediyl group whose valence bonds are from adjacent carbons. Illustrative of these compounds are the fl-mercaptoethanols of the formula:

(II) HORSH wherein R is as defined above, such as Z-mercaptoethanol, Z-mercaptopropanol, l-mercaptoisopropanol, l-mercapto- 2-methyl-2-butanol and the like; the [3,fi'-thiodialkanols of the formula:

(III) HORSROH wherein R is as defined above, such as 2,2'-thiodiethanol, 1,1'-thiobis(2-methyl-2-butanol) and the like; and the B43-(alkylenedithio)dialkanols of the formula:

(IV) HORSH SROH wherein R and R are as defined above, such as 2,2- (methylenedithio) dieth anol, 2,2- (ethylidenedithio diethanol, 2.2- trimethylenedithio) diethanol, 2,2- (tetramethylenedithio diethanol, 2,2- (isobutylidenedithio) diethanol, 2,2'- decamethylenedithio) diethanol and the like.

In addition, compounds which, under acidic conditions, hydrolyze to yield the compounds of Formula I, such as their diesters of carboxylic acids of up to 7 carbons, can also be employed. This broadened class can be represented by the formula:

(V) O O H (as...)

wherein m, n, R and R are as defined above, a is an integer having a value of from 0 to 6 inclusive; and x is an integer having a value of from O to l inclusive. Preferred diesters are those of carboxylic acids of from 1 to 2 carbons, i.e., the diformates and diacetates. Suitable esters include Z-mercaptoethanol diacetate, 2,2-thiodiethanol diacetate, 2,2'-(methylenedithio)diethanol diacetate and the like.

Impregnation of the fabrics with the polyepoxide, acidic curing agent and thiooxy compound can be effected in any suitable manner. It is prefered, however, to contact the fabric with an aqueous medium containing polyepoxide, acidic curing agent and thiooxy compound, as by spraying, padding and the like, The impregnated fabric is then dried and cured by heating at elevated temperatures.

The concentration of the various ingredients in the aqueous medium is not critical, and will vary depending upon the mode of application, because the sole criterion is the amount of each ingredient which is impregnated into the fabric being treated. Suitable amounts of polyepoxide and acidic curing agent are known to the art and, thus, form no part of this invention. The amount of thiooxy compound is critical, however, although it can vary depending upon the nature of the thiooxy compound. In general, as the amount of thiooxy compound increases the strength of the cured fabric increases but the efficacy of the treatment to provide wash and wear properties decreases. For the general class of compounds represented by Formula V, the amount of thiooxy compound applied to the fabric should be within the range of from about 0.1 to about 10 weight percent, based upon the weight of the dry fabric. As a general rule, the compounds containing free hydroxyl and/or mercapto groups of Formula I should be employed in amounts of less than about 2 weight percent. Their diesters, however, can be tolerated in much larger amounts, preferably in the range of from about 3 to about 7 weight percent.

The amount of acidic curing agent also has an effect on the maximum tolerable amount of thiooxy compound. That is, increasing amounts of thiooxy compounds can be tolerated as the amount of acidic curing agent is increased. For example, a formulation containing about 1.3 percent zinc fluoborate and 2.0 weight percent 2,2-thiodiethanol provides little improvement in Wash and Wear properties, but a significant improvement is observed when the concentrations of both zinc fluoborates and thiodiethanol are employed in amounts of about 2.0 weight percent. In both cases, however, the strength of the treated fabric is about the same.

Thus, by the term effective amount, as applied to the thiooxy compound, is meant that amount which provides significant improvement in fabric strength without serious reduction of the wash and wear properties of the fabric.

The thiooxy compounds can be employed in combination with any polyepoxide, including monomeric and polymeric polyepoxides, with monomeric diepoxides being preferred. Similarly, the acidic curing catalysts which can be employed are varied as desired.

The polyepoxides to be employed are materials possessing more than 1 vie-epoxy group, i.e., more than one group. They may be aliphatic, cycloaliphatic, aromatic or hetrocyclic and may be substituted if desired with noninterfering substituents, such as chlorine atoms, hydroxyl groups, ether radicals and the like. They may also be monomeric or polymeric.

For clarity, many of the polyepoxides, and particularly those of the polymeric type, will be described in terms of an epoxy equivalency. The term epoxy equivalency refers to the average number of epoxy groups, (i.e.,

groups) contained in the average molecule. This value is obtained by dividing the average molecular weight of the polyepoxide by the epoxide equivalent weight. The epoxide equivalent is determined by heating a one-gram sample of the polyepoxide with an excess of pyridinium chloride dissolved in pyridine. The excess pyridinium chloride is then back-titrated with 0.1 N sodium hydroxide to a phenolphthalein end point. The epoxide value is calculated by considering one HCl as equivalent to one epoxide group.

If the polyepoxide material consists of a single compound and all of the epoxy groups are intact the epoxy equivalency will be an integer, such as 2, 3, 4, and the like. However, in the case of polymeric-type polyepoxides many of the materials may contain some of the monomeric monoepoxides or have some of their epoxy groups hydrated or otherwise reacted and/or contain macromolecules of somewhat different molecular weight so the epoxy equivalency may be quite low and contain fractional values, The polymeric material may, for example, have an epoxy equivalency of 1.5, 1.8, 2.5, and the like.

The polyepoxides may be exemplified by the following: vinyl cyclohexene dioxide, epoxidized mono-, diand triglycerides, butadiene dioxide,

1,4-bis(2,3-epoxypropoxy)benzene,

1,3-bis(2,3-epoxyypropoxy)benzene,

4,4-bis(2,3-epoxypropoxy)diphenyl ether,

1,8-bis(2,3-epoxypropoxy)octane,

1,4-bis (2,3-epoxypropoxy) cyclohexane,

4,4-bis(2-hydroxy-3,4-epoxybutoxy)diphenyldimethylmethane,

1,3-bis(4,5-epoxypentoxy)-5-chlorobenzene,

1,4-bis(3,4-epoxybutoxy)-2-chlorocyclohexane,

diglycidyl thioether,

diglycidyl ether,

ethylene glycol diglycidyl ether,

resorcinol diglycidyl ether,

4 1,2,5 ,6-diepoxyhexyne-3 1,2,5,6-diepoxyhexane, 1,2,3,4-tetra(2-hydroxy-3,4-epoxybutoxy)butane, and 2,3-bis(glycidyloxy)-1,4-dioxane.

Other examples include the glycidyl polyethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess, e.g., 4 to 8 mol excess, of a chlorohydrin, such as epichlorohydrin and diglycerol chlorohydrin. Thus, a polyether which is substantially diglycidyl ether of 2,2-bis(2,3-epoxypropoxyphenyl) propane is obtained by reacting bis-phenol (2,2-bis(4-hydroxyphenyl)propane) with an excess of epichlorohydrin in an alkaline medium. Other polyhydric phenols that can be used for this purpose include resorcinol, catechol, hydroquinone, methyl resorcinol or polynuclear phenols, such as 2,2- bis(4-hydroxyphenyl)butane, 4,4 dihydroxybenzophenone, bis(4-hydroxyphenyl)ethane, and 1,5-dihydronaphthalene.

Still a further group of the polyepoxides comprises the polyepoxy polyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as hydrofluoric acid, one of the aforedescribed halogen-containing epoxides with a polyhydric alcohol, and subsequently treating the resulting product with an alkaline component. Polyhydric alcohols that may be used for this purpose include glycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentanetriol, pentaerythritol, diand tripentaerythritol, polyglycerol, dulcitol, inositol, carbohydrates, methyltrimethylolpropane, 2,6-octanediol, 1,2,4,5 tetrahydroxycyclohexane 2-ethylhexanetriol 1,2,6 glycerol methyl ether, glycerol allyl ether, polyvinyl alcohol and polyallyl alcohol, and mixtures thereof. Such polyepoxides may be exemplified by glycerol triglycidyl ether, mannitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether and sorbitol tetraglycidyl ether.

A further group of the polyepoxides comprises the polyepoxy polyesters obtained by esterifying a polycarboxylic acid with an epoxy-containing alcohol, such as, for example, the diglycidyl ester of adipic acid, the diglycidyl ester of malonic acid, and the diglycidyl ester of succinic acid.

Other polyepoxides include the polyepoxypolyhydroxy polyethers obtained by reacting, preferably in an alkaline medium, a polyhydric alcohol or polyhydric phenol with a polyepoxide, such as the reaction product of glycerol and bis(2,3-epoxypropyl)ether, the reaction product of sorbitol and bis(2,3-epoxy-2-methylpropyl)ether, the reaction product of pentaerythritol and 1,2 epoxy 4,5- epoxypentane, and the reaction product of bis-phenol and bis(2,3-epoxy-2-methylpropyl)ether, the reaction product of resorcinol and bis(2,3-epoxypropyl)ether, and the reaction product of catechol and bis(2,3-epoxypropyl)ether.

A group of polymeric-type polyepoxides comprises the hydroxy-substituted polyepoxy polyethers obtained by reacting, preferably in an alkaline medium, a slight excess, e.g., 0.5 to 3 mol excess, of a halogen-containing epoxide as described above, with any of the aforedescribed polyhydric phenols, such as resorcinol, catechol, bis-phenol, bis[4-(2'-hydroxynaphth-1-yl)-2,2-hydroxynaphth-1 yl] methane and the like.

Other polymeric polyepoxides include the polymers and copolymers of the epoxy-containing monomers possessing at least one polymerizable ethylenic linkage. When this type of monomer is polymerized in the substantial absence of alkaline or acidic catalysts, such as in the presence of heat, oxygen, peroxy compounds, actinic light, and the like, it undergoes additional polymerization at the multiple bond leaving the epoxy group unaffected. These monomers may be polymerized with themselves or with other ethylenically unsaturated monomers, such as styrene, vinyl acetate, methacrylonitrile, acrylonitrile, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, diallyl phthalate, vinyl allyl phthalate, divinyl adipate, 2-chloroallyl acetate, and vinyl methallyl pimelate. Illustrative examples of these polymers include poly(ally1 2,3-epoxypropyl ether), poly(2,3epoxypropyl crotonate), allyl 2,3-epoxypropyl etherstyrene copolymer, methallyl 3,4-epoxybutyl etherallyl benzoate copolymer, poly(viny1 2,3-epxypropyl)ether, allyl glycidyl ether-vinyl acetate copolymer and poly[4-(2,3'-glycidyloxy styrene] Acidic curing agents which are employed are the salts of (1) metals of Groups I to IV and VIII of the Periodic Table of Elements and (2) inorganic acids, the anion portion of which contains at least two dissimilar elements having an atomic weight about two, and particularly inorganic acids of the formula wherein X is a non-metal having an atomic weight above 2, Z is an element which tends to gain from 1 to 2 electrons in its outer orbit, such as oxygen and fluorine, w is an integer, z is an integer greater than 1 and y equals the valence of the radical (X) (Z) such as sulfuric acid, fluoboric acid, fluosilicic acid, persulfuric acid, phosphoric acid and the like.

Suitable salts include zinc fluoborate, magnesium fluoborate, magnesium perchlorate, potassium persulfate, copper fluoborate, copper persulfate, cobaltic fluoborate, chromic nitrate, magnesium nitrate, calcium phosphite, and the like.

Zinc fluoborate is the preferred curing agent, and is normally employed in combination with zinc oxide as a buffering agent. In general, the weight ratio of zinc oxide to zinc fluoborate is in the range of from about 0.05:1 to about 0.521, and preferably from about 0.111 to about 03:1.

The amount of curing agent is not highly critical, and can vary from about 0.5 weight percent to about 30 weight percent, based upon polyepoxide.

In addition to epoxide and organic thioether, the aqueous formulation may contain other ingredients known to improve the quality of wash and wear treatments, such as aldehydes, including formaldehyde or glutaraldehyde, urea, nitrogenous resins, fabric softeners; such as emulsified polyethylenes, and the like, anti-migration agents such as polyethylene glycols and the like. It is generally desirable to also provide a surfactant to ensure a uniform bath concentration and uniform wetting of the fabric to be treated.

Curing of the impregnated fabric is effected in any suitable manner, such as by heating at elevated temperatures in the range of from about 100 F. to about 400 F. A preferred technique comprises an initial drying step at about 150 F. to about 200 F. for about 1 to about 5 minutes, followed by a curing step at about 300 F. to about 350 F. for from about 1 to about 2 minutes. The preliminary drying step, although preferred, is not essential, and can be omitted if desired.

The following examples are illustrative. In the examples, the following tests were employed to evaluate the treated fabrics.

(1) Crease recovery angle.--Determined by ASTM Method D-1295-60 T, and reported as the sum of the angles in both the warp and filling directions.

(2) Wash-Wear Index.--Dete'rmined by AATCC tentative test Method 88-1961T employing washing procedure 3 (tumble dry) and omitting the tumble drying (spin dry), and employing evaluation procedure 2 (overhead illumination) with commercially-available threedimensional standards. Reported on a scale of 1 to 5 with 1 equivalent to very wrinkled and 5 equivalent to as ironed.

(3) Tear strength.Determined by ASTM D-1424-59 and reported in grams.

(4) Breaking strength.Determined by ASTM D- 1682-59T by the grab method in the filling direction at a rate of extension of 40% per minute and reported in pounds.

6 (5) Abrasion fiex.Determined by ASTM-1175-55T by the flexing and abrasion method in the warp direction and reported as the number of cycles to failure.

Example 1 A sample of cotton print cloth was padded to about 100 weight per cent wet pick up with an aqueous medium containing 5.0 weight percent 2,3-bis(glycidyloxy)-1,4-dioxane, 1.3 weight percent zinc fluoborate, 0.2 weight percent zinc oxide, 0.74 weight percent formaldehyde, 0.15 weight percent urea, 0.5 weight percent of a high molecular weight (15,000 to 20,000) polyethylene glycol marketed by Union Carbide Corporation under the trademark Carbowax 20M and employed as an anti-migration agent; 0.4 weight percent of a fabric softener marketed by C. H. Patrick Co. under the trademark Fabritone 23; and 0.1 weight percent of an ethylene oxide adduct of trimethylnonanol marketed by Union Carbide Corporation under the trademark Tergitol TMN as a surfactant. The impregnated fabric was then dried by heating at 175 F. for 3 minutes and cured by heating at 345 F. for seconds. Employing identical formulations and procedures, except that 2,2-thiodiethanol was present in the aqueous medium at a concentration of either 0.5 or 1.0 weight percent, two additional print cloth samples were impregnated, dried and cured. Each of the cured fabrics was evaluated for wash and wear properties (crease recovery angle and wash-wear index) and strength (tear strength and breaking strength). The data obtained by these experiments are summarized in Table I, below, with the data obtained by evaluation of untreated print cloth being included as a control.

These data, when converted to a percent retained basis, are summarized in Table II. For crease recovery angle, the basis is the value for the cured fabric treated with epoxide but no 2,2'-thiodiethanol (Run 1), and, for fabric strength, the basis is the strength of the control.

TABLE 11 Run No.

1 2 3 Control Percent Retained, Crease Recovery Angle:

ry 100 97 86 et 100 96 94 Tear Strength:

Warp 62 77 99 100 Filling 51 62 78 100 Breaking Strength 41 5Q 64 100 From the data of Table II it can be seen that increasing amounts of 2,2-thiodiethanol up to 1 percent considerably improve the strength of the treated fabric without a serious decline in wash and wear properties.

Example 2 Employing the techniques of Example 1, one sample of cotton print cloth was impregnated to about 100 percent wet pick up with an aqueous medium containing 7.0 weight percent 2,3-bis(glycidyloxy)-1,4-dioxane, 1.3 weight percent zinc fiuoborate, 0.2 weight percent zinc oxide, 0.15 weight percent urea, 0.4 weight percent Fabritone 23 and 0.1 weight percent Tergitol TMN, and cured by heating at 350 F. for seconds. A second sample of print cloth was impregnated with the same formulation, except that it also contained 2.0 weight percent thiodiglycol and then cured. The results of the evaluations of these fabrics are summarized in Table III.

This example illustrates that 2,2-thiodiethanol, if present in excessive amounts, can substantially stop the reaction of diepoxide with cotton, as is indicated by the low wash-wear index and low crease recovery angle.

Example 3 Employing formulations and techniques similar to those described in Example 1, except that 2,2'-thiodiethanol diacetate was substituted for 2,2'-thiodiethanol, several print cloth samples were impregnated, dried, cured and evaluated. The data obtained from these experiments are summarized in Table IV below.

TABLE IV Run No.

1 2 3 4 Control 2,2-thiodicthanol diacetate, percent. 1.1 2.3 4.6 Evaluation, Crease Recovery Angle:

Dry 256 251 233 234 177 ct 267 261 269 261 186 Wash-Wear Index:

Tumble Dry 5- 5 5- 4+ Spin Dry 3 3 2+ 2+ Tear Strength, gm

War 448 448 528 645 Filling 380 480 456 720 Breaki g Strength, lb 32 33 33 64 Percent Retained, Crease Recovery Angle:

Example 4 The experiments described in Example 1 were repeated, except that Z-mercaptoethanol was employed as the thiooxy compound. The results of these experiments are summarized in Table V.

TABLE V Run No.

1 2 3 4 Control Z-mercaptoethanol, percent 0 0.45 0. 9 1. 8 Evaluation, Crease Recovery Angle:

ry 256 245 222 191 177 ct 267 262 248 234 186 Wash-Wear Index:

Tumble Dry 5- 4+ 4- 3+ Spin Dry 3 3 2 2 Tear Strength, gm.:

Warp 552 704 680 645 Filling 512 696 784 720 Breaking Strength, lb 36 47 58 64 Percent Retained, Crease Recovery angle:

Dry 100 96 87 75 Wet 100 98 93 88 Tear Strength:

Warp 62 86 109 105 100 Filling 51 71 97 102 100 Breaking Strength 41 56 73 91 100 Example 5 A sample of cotton twill fabric was padded to 100 percent wet pick up with an aqueous medium containing 5.0 weight percent 2,3 bis (glycidyloxy) 1,4 dioxane, 1.3 weight percent zinc fluoborate, 0.2 weight percent zinc oxide, 0.74 weight percent formaldehyde, 0.5 weight percent Carbowax 20M, 0.4 weight percent Fabritone 23,

and 0.1 weight percent Tergitol TMN, dried by heating at 175 C. for 3.5 minutes and cured by heating at 305 F. for seconds. A second sample was impregnated with the same formulation, except that it also contained 0.5 Weight percent 2,2-thiodiethanol, and then dried and cured. The evaluations of these treated fabrics are summarized in VI.

TABLE VI Run No.

1 2 Control 2,2'-thiodiethanol, percent 0 0. 5 Evaluation, Crease Recovery Angle:

Dry 252 213 192 Wet 261 243 151) Wash-Wear Index, Tumble Dry 5 5 Breaking Strength, 11) 28 33 62 Percent Retained, Crease Recovery Angle:

Dry 84 Wet 100 93 Breaking Strength. 45 53 100 Example 6 The experiments of Example 5 were repeated except that 2,2-(isobutylidenedithio)diethanol was substituted for thiodiethanol. The results are summarized in Table VII.

Example 7 A sample of cotton twill fabric was padded to 100 percent wet pick up with an aqueous medium containing 7.0 weight percent of a commercially-available diepoxide marketed by Shell Chemical Corp. under the trademark of Eponite 100 having as the principal monomer 1,3-

' bis(glycidyloxy)isopropanol, 1.5 weight percent zinc fluoborate, 0.2 weight percent zinc oxide, 0.5 weight percent Carbowax 20M, 0.4 weight percent Fabritone 23 and 4.0 weight percent of a polyalkylene glycol ether marketed by Union Carbide Cor-p. under the trademark Tergitol XH, dried by heating at F. for 3.5 minutes and cured by heating at 305 C. for 90 seconds. A second sample of twill fabric was treated in an identical manner, except that the aqueous medium also contained 0.5 weight percent 2,2'-thiodiethanol. The evaluations of the cured fabrics are summarized in Table VIII.

Percent Retained, Crease Recovery Angle:

Example 8 A sample of cotton print cloth was impregnated with an aqueous medium containing 6.0 weight percent vinylcyclohexene dioxide, 3.0 weight percent of a commercially available triazone resin marketed by Rohm and Haas under the trademark Rhonite D-12, 3.0 weight percent of a commercially available dimethylolethylene urea resin marketed by Rohm and Haas under the trademark Rhonite 'R-l, 1.0 weight percent of zinc fiuoborate, 0.3 weight percent zinc oxide, 0.4 weight percent Fabritone weight percent 2,3-bis(glycidyloxy)-1,4-dixane, 1.5 weight percent zinc fluoborate, 0.2 weight percent zinc oxide, 0.74 weight percent formaldehyde, 0.5 weight percent Carbowax 20M, 0.4 weight percent of a polyeth- 23 and 0.2 weight percent, Tergitol TMN, dried by ylene emulsion marketed by Spencer Chemical Co. under heating at 175 F. for 3 minutes and cured by heating at 300 F. for 90 seconds. A second sample was treated in an identical manner, except that the aqueous medium also contained 0.5 weight percent 2,2'-thiodiethanol. Each the trademark Poly EM-40 as a fabric softener and 0.2 weight percent Tergitol TMN, dried by heating at 175 F. for 3.5 minutes and cured by heating at 350 F. for 90 minutes. Two additional samples of print cloth were fabric was then evaluated before and after laundering evaluated in an identical manner, except that the aqueous 2,2-thiodiethanol, wt. percent" Diethylene glycol, wt. percent.-. Evaluation, Crease Recovery Angle TABLE X Before After Laundering Laundering Run Number ry 272 177 Wet 277 186 Wash-Wear Index, Spin Dry- 4+ 4- Tear Strength, gm.:

War p 44g 384 432 416 645 Fllllng 360 296 264 336 309 720 Breaking Strength, lb 21 27 22 21 27 21 64 Percent Retained, Grease Recovery Angle:

Dry 101 104 100 104 99 101 100 98 with a commercially-available detergent. The results of these evaluations are summarized in Table IX.

TABLE 1X Before fter Laundering Laundering Run N0.

1 2 1 2 Control 2,2-thiodiethanol, percent. 0 0. 5 0 0. 5 Evaluation, Crease Recovery Angle:

Dry 276 264 247 248 177 W 245 243 260 253 186 Wash-Wear Index, Spin Dry 1 4 4 Tear Strength, gm.:

Warp 544 616 488 520 645 Filling r. 688 688 528 582 720 Breaking Strength, lb 38 43 39 45 64 Percent Retained, Crease Recovery Angle:

ry 100 96 100 100 Wet 100 99 100 97 Tear Strength:

Warp 84 96 75 81 100 Filling 96 96 73 81 100 Breaking Strengt 59 67 61 70 100 1 Average of the ratings after each of two successive launderings.

Example 9 A sample of cotton print cloth was padded to 100 per- Example 10 A sample of cotton broadcloth was padded to about 100 percent Wet pick up with an aqueous medium containing 5.0 weight percent 2,3-bis(glycidyloxy)-1,4-dioxane, 1.3 weight percent zinc fluoborate, 0.2 weight percent zinc oxide, 0.74 weight percent formaldehyde, 0.5 weight percent Carbowax 20M, 0.4 weight percent F abritone 23 and 0.1 weight percent Tergitol TMN, dried by heating at 115 F. for 3.5 minutes and cured by heating at 305 F. for seconds. A second sample of broadcloth was treated in an identical manner, except that the aqueous medium also contained 0.5 weight percent 2,2'-thiodiethanol. Additional sets of cured fabrics were produced in the same manner, except that curing was effected at 325 F. or 345 F. instead of 305 F. The evaluations of 55 cent wet p1ck up with an aqueous medium containing 5.0 each of these fabrlcs are summarized in Table XI.

TABLE XI Run Number 1 2 3 4 5 6 Control Cure Temp., F 305 30 325 325 345 345 2,2'-thiodiethanol, percent 0 0. 5 0 0. 5 0 0. 5 Crease Recovery Angle:

Dry 267 263 257 260 272 263 168 Wet 264 260 274 270 271 250 178 Wash-Wear Index:

Tumble Dry 5- 5- 5 5- 5 5- Spin Dry 3+ 3- 4- 4- 4- 4 Tear Strength, g.m:

Warp 400 448 360 432 352 416 728 504 352 432 336 440 760 32 22 28 21 27 57 Abrasion Flex 627 233 511 237 647 492 Percent Retained, Crease Recovery Angle:

Dry 98 100 101 100 97 Wet 100 99 100 99 100 92 Tear Strength:

Warp 55 62 49 59 48 57 100 Filling 53 66 46 57 44 58 100 Breaking Strength 47 56 39 49 37 47 100 Abrasion Flex 73 127 47 104 48 182 100 A sample of cotton broadcloth was padded to about 100 percent wet pick up with an aqueous medium containing 7.0 weight percent 2,2'-thiodiethanol, 2.0 weight percent zinc fluoborate, 0.3 weight percent zinc oxide, 0.5 weight percent Carbowax 20M, 0.4 weight percent Fabritone 23 and 0.1 weight percent Tergitol TMN, dried by heating at 175 F. for 3.5 minutes and cured by heating at 345 F. for 90 seconds. The evaluation of the treated and the untreated fabrics are summarized in Table XII.

TABLE XII Run No 1 Control Crease Recovery Angle:

Dry 207 168 Wet 222 178 Wash-Wear Index:

Tumble Dry 1 Spin Dry..." Tear Strength, gm

Fillin g Breaking Strength, 1b

Employing similar techniques, a sample of cotton print cloth was padded to 100 percent wet pick up with an aqueous medium containing 0.5 weight percent 2,2'-thiodiethanol, 7.0 weight percent 2,2'-thiodiethano1 diacetate, 1.3 weight percent zinc fluoborate, 0.2 weight percent zinc oxide and 0.15 weight percent urea, dried and cured. The evaluation of the treated and untreated fabrics are summarized in Table XIII.

As can be seen from the data presented in Tables XI and XII, the thiooxy compounds of this invention, when employed in the absence of polyepoxides, do provide a slight improvement in wash-and-wear properties, but seriously reduce the strength of the treated fabric, thus illustrating the necessity of a combination of polyepoxide and thiooxy compound to achieve both good wash and wear properties and good strength retention.

What is claimed is:

1. In the method for improving the wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 0.1 to about 10 weight percent, based on the weight of the dry fabric of a thiooxy compound of the formula:

A L\ m J. A wherein a is an integer having a value of from to 6, inclusive; each of m, n and x independently is an integer having a value of from 0 to 1, inclusive; R is an a,/3-alkanediyl group of from 2 to 6 carbons; and R is an alkanediyl group of from 1 to 10 carbons.

2. The cured fabric as produced by the process of claim 1.

3. In the method for improving the wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 0.1 to about 2 weight percent based on the weight of the dry fabric of a thiooxy compound of the formula:

wherein each of m and n independently is an integer having a value of from 0 to 1, inclusive; R is an a e-alkanediyl group of from 2 to 3 carbons; and R is an alkanediyl group of from 1 to 6 carbons.

4. The cured fabric as produced by the process of claim 3.

5. In the method for improving the wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 0.1 to about 2 weight percent based on the weight of the dry fabric of 2,2- thiodiethanol.

6. The cured fabric as produced by the process of claim 5.

7. In the method for improving the wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 0.1 to about 2 weight percent based on the weight of the dry fabric of 2-mercaptoethanol.

8. The cured fabric as produced by the process of claim 7.

9. In the method for improving the wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 0.1 to about 2 weight percent based on the weight of the dry fabric of 2,2- (isobutylidenedithio)diethanol.

10. The cured'fabric as produced by the process of claim 9.

11. In the method for improving the Wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 3 to about 7 weight percent based on the weight of the dry fabric of a diester of a carboxylic acid of from 1 to 2 carbons and from about 0.1 to about 2 percent based on the Weight of the dry fabric of a thiooxy compound of the formula:

wherein each of m and n independently is an integer having a value of from 0 to l, inclusive; R is an a,fi-alkanediyl group of from 2 to 3 carbons; and R is an alkanediyl group of from 1 to 6 carbons.

12. The cured fabric as produced by the process of claim 11.

13. In the method for improving the wash and wear properties of a cellulosic fabric by impregnating said fabric with an aqueous medium containing a polyepoxide and an acidic curing agent therefor and thereafter curing the impregnated fabric, the improvement of incorporating in said aqueous medium from about 3 to about 7 weight percent based on the weight of the dry fabric of 2,2- thiodiethanol diacetate.

14. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting essentially of an aqueous medium containing a polyepoxide, an acidic curing agent therefor and from about 0.1 to

about 10 weight percent based on the weight of the dry fabric of a thiooxy compound of the formula:

l, A J a /x wherein a is an integer having a value of from to 6, inclusive; each of m, n and x independently is an integer having a value of from 0 to l, inclusive; R is an cap-alkanediyl group of from 2 to 6 carbons; and R is an alkanediyl group of from 1 to 10 carbons.

15. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting essentially of an aqueous medium containing a polyepoxide, an acidic curing agent therefor and from about 0.1 to about 2 weight percent based on the weight of the dry fabric of LC l HORS L\R S/m ROJDH wherein each of mand n independently is an integer having a value of from 0 to l, inclusive; R is an u,fl-alkanediyl group of from 2 to 3 carbons; and R is an alkanediyl group of from 1 to 6 carbons. 1

16. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting essentially of an aqueous medium containing a polyepoxide, an acidic curing agent therefor and from about 0.1 to about 2 weight percent based on the Weight of the dry fabric of 2,2-thiodiethanol.

17. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting es sentially of an aqueous medium containing a'polyepoxide, an acidic curing agent therefor and from about 0.1 to about 2 weight percent based on the weight of the dry fabric of Z-mercaptoethanol.

18. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting es sentially of an aqueous medium containing a polyepoxide, an acidic curing agent therefor and from about 0.1 to about 2 weight percent based on the weight of the dry fabric of 2,2-(isobutylidenedithio)ethanol.

19. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting essentially of an aqueous medium containing a polyepoxide, an acidic curing agent therefor and from about 3 to about 7 weight percent based on the weight of the dry fabric of a diester of a carboxylic acid of from 1 to 10 carbon-s and from about 0.1 to about 2 weight percent based on the weight of the dry fabric of a thiooxy compound of the formula:

I7 "l R R R 5 /m .1:.

wherein each of m and n independently is an integer having a value of from 0 to l, inclusive; R is an u,B-alkanediyl group of from 2 to 3 carbons; and R is an alkanediyl group of from 1 to 6 carbons.

20. A composition for treating a cellulosic fabric to improve its wash and wear characteristics consisting essentially of an aqueous medium containing a polyepoxide, an acidic curing agent therefor and from about 3 to about 7 weight percent based on the weight of the dry fabric of 2,2'-thiodiethanol diacetate.

References Cited UNITED STATES PATENTS 2,988,417 6/1961 Emmons et al. 8-116 LEON D. ROSDOL, Primary Examiner J. D. WELSH, Assistant Examiner US. Cl. X.R. 

